GB2078230A - Thiomolybdenum derivatives of dispersant alkenylsuccinimides and lubricants containing same - Google Patents
Thiomolybdenum derivatives of dispersant alkenylsuccinimides and lubricants containing same Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/18—Complexes with metals
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
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- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
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Abstract
Thiomolybdenum dispersants can be formed by reacting an alkenylsuccinimide (A) of the formula: <IMAGE> wherein R is an alkenyl radical having from 50 to 200 carbon atoms in the chain and x is 0 to 10, with (B) an ammonium salt of a molybdenum thioacid e.g. ammonium tetrathiomolybdate or (C) a molybdenum oxyacid and hydrogen sulfide and removing any volatile by-products. The thiomolybdenum dispersants can be incorporated in lubricating oils to improve anti-wear properties and provide friction reduction and oxidation stability.
Description
SPECIFICATION
Thiomolybdenum derivatives of dispersant alkenylsuccinimides and lubricants containing same
This invention relates to novel additives serving to impart dispersant, anti-wear, oxidation inhibition and friction reducing properties to lubricating compositions.
Compounds of the type disclosed herein have not been used previously in lubricating compositions. In the closest art known to us, U.S. Patent No. 3,010,902 describes lubricant additives consisting of the product obtained by reacting sulfur and an unsaturated alcohol or an organic base having hydrocarbon radicals and then reacting a molar excess of the resulting compound with molybdenum blue, a mixed oxide having the formula MoO2.4 MoO3.6H20. By contrast, the present compounds are prepared either by generating an inorganic thiomolybdenum compound prior to its reaction with the dispersant or by treating an oxymolybdenum-dispersant complex with hydrogen sulfide.
In accordance with this invention, it has been surprisingly discovered that a composition of matter consisting essentially of the reaction product of an alkenyl-succinimide of the formula:
wherein R is an alkenyl radical having from 50 to 200 carbon atoms in the chain, and x is an integer ranging from 0 to 10, with 0.1-10 atomic equivalents of molybdenum from either (1) a sulfurmolybdenum compound or (2) from a molybdenum compound and H25 has outstanding properties as a lubricant additive. The starting succinimide can be preformed or formed in situ.
The invention also provides a lubricant containing from 1 to 55 weight percent of the above composition, the balance a mineral oil of lubricating viscosity.
From their chemical analysis and on the basis of their preparation, the products of the invention are believed to have structures such as the following:
wherein n = 1 to 10 (reflecting Mo anions ranging from MoO4 to a polymolybdate with 10 Mo atoms), x=Oto 10,y= 1 to4,z=3 toO and m = 1 to 10, but not greater than x + 1.
Structures of the following type are examples of a second possibility involving covalent bonding of
Mo to N:
where I = 1 to 5, p = 0--2, and x, y, z and n have the preceding values. Also structures are believed to exist where the Mo moiety is covalently linked to two or more alkenylsuccinimide moieties.
In the above structures, the Mo-containing units and the ethylene mine units may be interspersed randomly or they may be sequential, and the Mo-containing units may also be terminal with the ethylene mine units located close to the succinimide ring.
The molybdenum moiety may possess either only one Mo atom, or two or more Mo atoms which are bridged by S or 0 atoms to form cyclic or polymeric species.
The preparation of the reaction product used in a lubricating composition according to the invention is relatively uncomplicated and can be economically conducted.
The composition of the invention consists essentially of products obtained by the following reactions. Although the following reactions illustrate the use of commercially available or easily preparable hexavalent molybdenum compounds, lower-valent molybdenum compounds also can be used without unduly affecting the properties of the resulting products.
In one, a thiomolybdate derivative of an alkenylsuccinimide of a polyamine, having the formula given above where preferably R is polyisobutenyl of a molecular weight of about 700-3000 (preferably about 1220), and x is 1-1 0 (preferably 2-4) is prepared by: (1) reaction of an aqueous solution containing 0.1-10 (preferably 1-2) molar amounts of ammonium tetrathiomolybdate with one mole of the succinimide in a hydrocarbon solvent; (2) removal of the water by azeotropic distillation, simultaneously removing ammonia and a minor part of the sulfur as hydrogen sulfide; (3) filtering, and (4) stripping off the organic solvent at reduced pressure. The product is shown to have dispersancy, oxidation inhibition, and exceptional friction reducing properties in lubricants.
In a second preparative procedure, a thiomolybdenum derivative of an alkenylsuccinimide is prepared by: (1) reaction of 0.1-10 (preferably 1-2) atomic equivalents of Mo from an aqueous "molybdic acid" solution (prepared by nonreductive acidification of aqueous Na2MoO4) with an alkenylsuccinimide of a polyamine, as above defined, dissolved in a mixed solvent composed of a hydrocarbon and an ethylene glycol-based ether, which may have either hydroxyl alkyl ether or aryl ether termini, (2) treatment of the intermediate molybdenum: succinimide reaction product with approximately 4 moles H2S per mole of Mo; (3) removal of the water by azeotropic distillation; (4) filtering and (5) stripping off solvents at reduced pressure. The resulting product has dispersancy, antiwear, and excellent friction reducing properties.
The second preparative procedure can be varied in that (1) a minor percentage of a non-volatile polyglycol derivative (alkylphenyl ether) is used in place of the ether solvent and (2) only about 1 to 2 moles of H2S per mole of Mo are charged. Preferably the polyglycol is an alkylphenyl ether of ethylene glycol or of a polyethylene glycol or a mono-nonylphenyl ether of ethylene glycol or of a polyglycol containing 2 to 10 oxyethylene units. The product resulting from this variation has oxidation inhibition, dispersancy and excellent friction reducing properties.
In another modification, thiomolybdenum derivatives of an alkenylsuccinimide can be prepared from an ammonium thiomolybdate intermediate generated in-situ by mixing the succinimide with an aqueous solution of an ammonium salt of an oxymolybdic acid followed by treatment with hydrogen sulfide employing a mole ratio of hydrogen sulfide to molybdenum of 1:1 to 4:1.
in a still further modification, the thiomolybdenum derivatives are obtained when the aqueous solution of an ammonium salt of the oxymolybdenum acid is generated by the reaction of molybdenum trioxide with at least one mole of aqueous ammonium hydroxide.
In another modification, the sulfur molybdenum compound is generated in situ by contacting the succinimide with water, molybdenum trioxide and less than the stoichiometric amount of ammonium hydroxide, preferably, from 0.1 to 0.5 mole of NH4OH per mole of molybdenum followed by treating with hydrogen sulfide using a mole ratio of H2S: Mo of 1:1 to 4:1.
Modifications can be varied by (1 ) employing a minor percentage of a non-volatile polyglycol ether, (2) omitting the volatile hydrocarbon solvent; (3) removing water by heating under an inert gas 100 to 1 500C, optionally, completing water removal by application of reduced pressure at the elevated temperature.
As above noted, the reactions according to the process are conducted in the absence of catalyst but generally in the presence of a solvent or diluent or mixture thereof to facilitate the reaction. Solvents are removed in the latter stages of the process; the diluents or non-volatile ether components are compatible with lubricating oils.
In order to more fully illustrate the nature of the invention and the manner of practicing the same, the following examples are presented as representative of its best mode.
EXAMPLE I
Preparaton of Thiomolybdenum Derivatives of an Alkyl-Succinimide from Ammonium
Tetrathiomolybdate
A suspension (partial solution of 13.50 g. (about 0.05 mole (NH4)2MoS4 in 50 ml. water was stirred into a solution of 340.0 g. (0.06 mole) of a 50% oil concentrate of a polybutenylsuccinimide of triethylenetetramine in 200 ml. cyclohexane. This mixture was heated to reflux under N2, and the water was removed by azeotropic distillation into a Dean-Stark trap. After 2 hrs. at 73-1 000C., the waterfree reaction mixture was filtered at room temperature, and then distilled to remove solvent to 1 00 C.
at about 10 mm. The yield was 346 g. of a clear, deep brown product which had the following analyses.
%Mo = 1.04, %N = 0.90, %S = 0.83. The atomic ratio of S:Mo was calculated from these analyses to be 2.40.
EXAMPLE II
Thiomolybdenum Derivative of an Alkenylsuccinimide Via Thiomolybdate Intermediate Prepared In-Situ
A solution of 24.20 g. (0.1 mole) Na2MoO4.2H20 in 25 ml. water was treated with 10.0 g. (0.1 mole) of conc. H2S04,followed by addition of 100 ml. diethyleneglycol dimethylether (Diglyme). To the resultant solution of this "molybdic acid" was added a solution in 500 ml. cyclohexane of 583.3 g.
(about 0.1 mole) of the polybutenylsuccinimide of triethylenetetramine used in the previous example.
After stirring 1/2 hour at ambient temperature, hydrogen sulfide was bubbled through the mixture at 75 ml./min. (about 0.2 mole/hr.) for 2 hours. The deep orange mixture was heated to reflux, and the water
was removed by azeotropic distillation over 2-1/2 hr. at 7893 C. The mixture was cooled and filtered
to remove the Na2 SO4 byproduct and other insolubles. The filtrate was stripped to remove solvents up
to 800coat about 10 mm, yielding 609 g. product. The analyses were as follows: %Mo = 1.53 (= theoretical), %N = 0.82, %S = 1.10, and %Na = 0.1 7. The atomic ratio of S:Mo was calculated = 2.16 (vs. 4:1 for the charge).
EXAMPLE Ill
Thiomolybdenum Derivative of an Alkenylsuccinimide via a Thiomolybdate Intermediate Prepared In
Situ in the Presence of an Ethoxylated Phenolic Compound
The same materials and procedure were used as in Example 2, except (1) the "Diglyme" co
solvent was replaced by 12.0 g. of Surfonic N-60 (a polyethoxylated nonylphenol from Jefferson
Chemical Co.), and (2) only one-half as much H2 S was charged by employing the previous rate but for
only 1 hr. (instead of 2). The yield of product = 594 g.; its analyses were as follows: %Mo = 1.36, %S = 0.87, %N = 0.93, and %Na = 0.16. The S:Mo mole ratio was calculated = 1.9:1, essentially equal to the charge ratio.
EXAMPLE IV
Improved Process for Preparation of a Thiomolybdenum Derivative of an Alkenylsuccinimide
This process differs from the preceding example in that no volatile organic solvent is used, and
water is removed by N2 blowing to a more elevated temperature.
A mixture of 561.7 g. (0.1 mole) of a 50% oil concentrate of a polybutenylsuccinimide of
triethylenetetramine and 12.0 g. of a polyethoxylated nonylphenol is heated in a reaction flask to 80 C. Then a "H2MoO4,, solution is prepared by addition of 10.0 g. (0.1 mole) conc. H2S04 to 24.2 g.
mole) Na2MoO4.2H20 in 50 ml. water and added to the reaction flask. This stirred mixture is blown with H2 S at 75 milmin around 0.2 mole-hr.) at 80--900 for 2 hours. The H2S is shut off, and the mixture is
blown with N2 while heating to 1 500C, removing the water. After 2 hours at 1 500, approximately 10
mm. vacuum is applied for 1/2 hour at 1500. The reaction mixture is then filtered at about 120--1300, removing the Na2SO4 by-product. The recovery was 524 g. The analyses were as follows: %Mo = 1.5,
1.6, %N = 0.90; %S = 1.24, 1.40; and %Na = 0.24.The molybdenum conversion was essentially
quantitive and the mole ratio of S:Mo is calculated from the analyses = 2.44:1.
EXAMPLE V
Preparation of Thiomolybdenum Derivatives of an Alkenylsuccinimide from an Ammonium
Thiomolybdate Intermediate Generated In-Situ
A solution of an ammonium molybdate is prepared by adding 12 ml. (about 0.18 mole) of
concentrated ammonium hydroxide to a stirred mixture of 10.80 g (0.075 mole) molybdenum trioxide
and 20 ml. of water, and stirring 1 5 minutes at 5565C. The resultant solution is added to a preheated (to 65 ) mixture of 420 g. (0.075 mole) of a 50% oil concentrate of a polybutenylsuccinimide of triethylene tetramine and 8.4 g. of "Surfonic N-60" (a polyethoxylated vinylphenol from Jefferson
Chemical Company).The reaction mixture is then heated to 80C and hydrogen sulfide is bubbled through the mixture at 56 ml/min. (about 0.15 mole/hr) for 1 hour at 80--850. The H2S is shut off, and the mixture is blown with N2 while heating to 150 , removing the water, ammonia, and a minor amount of H2S. After continuing to blow with nitrogen at 1 soy for 2 hours, the almost clear product was filtered at about 120-1 50C; the yield was 387 g. of a clear, brown product. The analyses were as follows: %Mo = 1.26, %N = 1.00, and %S = 0.77. The S:Mo mole ratio is calculated from the analyses as being 1.83:1.
EXAMPLE Vl This example describes the preparation of thiomolybdenum derivatives of an alkenylsuccinimide from an ammonium thiomolybdate intermediate generated in-situ in a one-pot process using a much less than stoichiometric amount of ammonium hydroxide.
The same materials are used as in Example V except that 40 ml. water and only 1.0 ml. (about 0.015 mole) of concentrated ammonium hydroxide are used. This procedure differs from Example V, as follows.
The mixture of alkenylsuccinimide and polyethoxylated alkylphenol is heated to 65 , and then 35 ml. water and the MoO3 are added successively. This mixture is heated over 1 hr. to 80 , and then a solution of 1 ml. of concentrated NH4OH and 5 ml. water is added. This mixture is blown with hydrogen sulfide and then stripped under nitrogen as in Example V. The product filters well at 120--1500, yielding a clear product. The analyses were as follows: %Mo = 1.22, %S = 1.00, %N = 0.76 (probably an error in analyses. Approximately 1 .0%N is expected). The mole ratio of S:Mo is calculated from the analyses = 2.46:1.
EXAMPLE VII
This example describes the preparation of thiomolybdenum derivatives of an alkenylsuccinimide
from an ammonium thiomolybdate solution generated by reaction of an aqueous ammonium sulfide
solution and molybdenum trioxide. This procedure differs from Example I in that a crude ammonium
thiomolybdate having an average stoichiometry of about 2:1 S:Mo is prepared by adding 10.80 g.
(0.075 mole) molybdenum trioxide to a solution of 19.6 g. (about 0.1 5 mole) of a concentrated
ammonium sulfide (5260%) solution and 35 ml. water. The resultant solution/suspension is added to a mixture of 525 g. (about 0.094 mole) of a 50% oil concentrate of a polyisobutenylsuccinimide of triethylenetetramine and 10.5 g. polyethoxylated alkylphenol. The final reaction mixture is stirred 1 hr.
at 75C before N2-blowing to 150 , removing water, ammonia, and a minor amount of hydrogen sulfide.
After 2 hrs at 1 soy, the mixture is filtered at 120--1 500 to obtain a clear, brown product. The analyses
obtained were 1.14%Mo, 0.96%N, and ).91 %S. The S:Mo atomic ratio is calculated from the
analyses = 2.39.
EXAM P LE Vl l l This example describes a process for preparing a thiomolybdenum derivative of an
alkenylsuccinimide using a molybdenum oxyacid and hydrogen sulfide as the only other reagents.
In carrying out this procedure, a mixture of 420 g. (0.075 mole) of a 50% oil concentrate of a
polybutenylsuccinimide of triethylenetetramine (polybutenyl group derived from an 1300 mol. wt.
olefin) and 8.4 g. of a polyethoxylated nonylphenol is heated in a reaction flask under N2 to 650. Then 30
ml. water and 10.80 g. (0.075 mole) molybdenum trioxide are added, and the mixture is stirred 1/2 hour
at 65 , followed by being heated to 800. Then hydrogen sulfide gas is bubbled at 56 ml/min. (-0.15 mole/hr) through the stirred mixture at 8085 for 1 hour. The H20 is then shut off and the mixture is
blown with N2 at 50 ml/min. while being heated to 1 soy, removing water and excess H2S. After 2 hours at SOC, the hot mixture is filtered (at 1 50-1 20C) to remove the minor amount of insolubles present.
This is in contrast to Example IV, where large amounts of sodium sulfate by product must also be
removed.
The filtered product of this example had the following analyses: %Mo = 1.50, %N = 0.94,
%S = 1.09. The Mo conversion was 93% and the atomic ratio of S:Mo is calculated from the
analyses = 2.18:1.
EXAMPLE IX
This example illustrates a process modification of Example 1 in which the surfactant, a
polyoxyethylated nonylphenol, is omitted. In conducting this preparation, the same materials are used as
in Example VEIL, except for omitting the polyethoxylated nonylphenol. Following the identical reaction procedure, a filtered product is obtained with the following analyses: %Mo = 1.52, %S = 1.08, and %N = 0.99. These results are essentially identical to those of the product of Example VIII.
EXAMPLE X
This example shows a "one-pot" process for preparation of a thiomolybdenum derivative of an
alkenylsuccinimide in which the alkenylsuccinimide is prepared in situ at 11 or. To a mixture of 10.95 g.
(0.075 mole) triethylenetetramine and 138 g diluent oil (100 E Pale Stock HF) stirred at 6or, 199.0 g.
(0.083 mole) of an approximately 1 400 molecular weight polybutenylsuccinic acid anhydride (which
contains about 18% diluent oil) is added over 1/2 hour at 6080 . The reaction mixture is heated with N2-blowing at about 50 ml/min. to 1100., removing the water of reaction to a major extent. After 2
hours at 1 lox., the oil concentrate of the alkenyl-succinimide thus produced is allowed to cool while (1)
7.0 g. polyoxyethylated nonylphenol, (2) 30 ml. water (at 100 ), and (3) 10.80 g. (0.075 mole)
molybdenum trioxide are added.This mixture is stirred 1/2 hour at 95C and then it is blown with
hydrogen sulfide at 56 ml/min. (0.15 mole/hr) for 1 hour at 950.
The filtered product had the following analyses: %Mo = 1.68, %N = 1.03, and %S = 1.04. The Mo conversion was 86%, and the atomic ratio of S:Mo = 1.86.
EXAMPLE Xl
This example shows a modification of the previous process in which the alkenylsuccinimide is
prepared in situ at 950.
This preparation uses the same materials (and quantities) as in Example X and the procedure is
identical, except that the initial amine, diluent oil, alkenylsuccinic acid anhydride mixture is heated at
950 for 2 hours (instead of 1100). Then the water and MoO3 are charged at 950 and the last part of the
procedure is completed exactly as in Example X.
The filtered product of this example had the following analyses: %Mo = 1.68 (identical to Example
IX), %N = 1.06, and %S = 1.38. The Mo conversion was 86% and the atomic ratio of S:Mo = 2.46.
Lubricating compositions according to the present invention contain at least one of the above
products in an amount ranging from about 0.01 to 55.0 percent; preferably between 0.1 and 15.0
percent by weight and especially at least 0.5 to 10.0 percent by weight. Alternatively, amounts to provide from about 0.01 to 5.0 percent by weight of molybdenum, 0.03 to 0.15 percent by weight, and
0.05 to 0.08 percent by weight are the preferred ranges.
The present compositions can also contain a combination of other well known additives in an amount sufficient to achieve each additive's function.
Lubricating compositions according to this invention comprise a major amount of any of the well
known types of oils of lubricating viscosity as suitable base oils. They include hydrocarbon or mineral lubricating oils or naphthenic, paraffinic and mixed naphthenic and paraffinic types. Such oils may be refined by any of the conventional methods such as solvent refining and acid refining. Synthetic hydrocarbon oils of the alkylene polymer type or those derived from coal and shale may also be employed. Alkylene oxide polymers and their derivatives such as the propylene oxide polymers and their ethers and esters in which the terminal hydroxyl groups have been modified are also suitable. Synthetic oils of the dicarboxylic acid ester type including dibutyl adipate, di-2-ethyl-hexyl sebacate, di-n-hexyl fumaric polymer, dilauryl azelate, and the like may be used.Alkyl benzene types of synthetic oils such as tetradecyl benzene, etc., are also included.
The oil blends of the products of the above example were tested by various tests. Of these, the
Bench VC Test, above mentioned, measures turbidity, the lower the turbidity values indicated below the better dispersancy. This test is carried out by mixing together exact volumes of the test oil, a synthetic blowby, and a mineral oil diluent in a test bottle. The bottle is then placed on a rocker and rocked for four hours at 1 38CC. After heating, the sample is diluted with more mineral oil, cooled to room temperature, and the sample's turbidity is measured with a Lumetron turbidimeter equipped with a 700 millimicron filter. Synthetic blowby is a hydrocarbon fraction which has been oxidized under specific conditions. This material emulates the oxidized compounds which find their way past the piston rings and into the crankcase of an internal combustion engine.
The Bench L-38 Test simulates in a journal bearing rig, the conditions which are produced in the engine test of Federal Method No. 791 a, Method 3405.1, and provides a method for studying the copper-lead bearing corrosion characteristics of crankcase oils. The copper strip test is based on ASTM
Method D--l 30 and involves immersing a polished copper strip in a given quantity of neat oils and oils containing the additive under test and heating for a temperature and time characteristic of the material being tested. At the end of this period the copper strip is removed, washed and compared with the
ASTM Copper Strip Corrosion Standards.
The third test employed was the Four Ball Wear Test described in U.S. Patent No. 3,384,588 which measures the amount of wear a lubricating oil permits under engine test conditions with and without additives to be tested. The greater amount of wear, the poorer the ability of the test oil composition to prevent such wear. This wear is measured in terms of the wear scan diameter. This test was run here for 2 hours at 600 rpm/93 C/40 kg load. The friction coefficient was measured at the end of the test when the anti-friction film is fully developed.
The Small Engine Friction Test is a single cylinder engine test which measures the frictional characteristics of an oil. The values given in Table I are based on the torque required to motor an engine
containing the oil under test. The results of this test have been found to correlate with field experience using a large fleet of cars under varied on-the-road driving conditions as the percentage change in torque correlates with a percent change in fuel economy.
The Bench IIID Test measures the oil thickening tendencies of motor oils under high temperature conditions. The test consists of oxidizing a sample of oil in the presence of air with an iron and copper
catalyst at 171 CC. After 24, 48 and 72 hours the percent increases in viscosity at 400C and milliliters evaporation loss are determined on the oxidized oil. After 24 and 48 hours fresh make-up oil is added to
the oxidized oil.
TABLE 1
Test Oll Formulation (1) 4-Ball Test
Test Olls
Containing Copper Strlp Bench IIID Test Bench Bench Small Engine
Product of Mo Additive Succinimide Corr. Test % Vis. Inc Wear, Friction VC Friction Test
Ex. No. Wt. % (%Mo) 300 /3 Hrs. at 72 hrs. mm. Coefficient Test % Fric. Red'n.
None 8.0 1A Too viscous 0.41 0.095 2.0 26.6 0#2
to measure
I 8.0 (0.085) 0 1B 91 0.37 0.075 5.0 - 25
II 5.2 (0.07) 3.0 1A - 0.34 0.079 4.0 24.5 21
III 5.9 (0.08) 2.0 1A 94 - - 3.5 17.6 20.17
IV 5.9 (0.08 2.0 2A 95 0.33 0.071 - -
V - - - - - - - 21.3
VII 6.16 (0.08) 2.0 1A 4.5 15
XI - - - - - - - 18.9 (1) The test oils were 10W-40 grade oils also containing a succinimide dispersant, a zinc dialkyldithiophosphate, an overbased calcium sulfonate, an aromatic secondary amine, an ashless rust inhibitor, a VI improver, a pour point depressant, and an anti-foam agent.
From the data of Table I, it is seen that the additives of the invention are effective for enhancing the
properties of lubricating oils. Thus, the product of Example 1 improves the oxidation stability of the test oil in the Bench ILIAD Test, improves the ability of the test oil to prevent wear by about 10 percent in the 4-Ball and reduces friction by 25 percent. The additives of Examples 3 and 4, which impart about the same (0.08%) Mo content to the oils though used in lesser total weight percentages, and the additive of
Example 2, which imparts only 0.07% Mo, all produce substantially the same results on most of the tests and perform similarly in the 4-Ball Test.The results of the copper strip corrosion test and of the
Bench L-38 Test show that these sulfur-bearing molybdenum additives do not decrease (and may possibly improve) the corrosion resistance of the formulated oils. It should be noted that the test oils were fully formulated oils containing the additives mentioned in footnote (1), yet the data show that even a fully formulated oil can be improved in anti-wear, friction reduction and oxidation stability by the incorporation therein of the additives of the invention. This is quite surprising and unexpected.
The test results in Table II show that the Example 4-type thiomolybdenum derivative of an alkenyl (PIB)-succinimide of triethylenetetramine (TETA) has oxidation and corrosion inhibiting properties in the absence of the conventional additives normally used for these purposes.
Oil blends A and B compare the effects of the Example 4 additive vs. its parent succinimide in the absence of the usual anti-oxidants. The data show that the Example 4-type additive supplied an excellent anti-oxidant effect. In Blend C, the added anti-oxidant had the expected effect. In Blend D, where the zinc dialkyldithiophosphate was omitted, both oxidation and corrosion inhibition surprisingly were still excellent.
TABLE II
Performance of Additives as Oxidation
and Corrosion Inhibitors vs. Conventional Additives
Oil Blend A B C D
Composition, Wt. % (1)
Ex. 4 Additive (% Mo /%N) - 4.2 (.06 1.04) 4.2 4.2
PIB Succinimide of TETA (%N) 4.0 (.04) -
Zinc Dialkyldithiophosphate 0.5 0.5 0.5 0
Aryl amine (oxidation inhibitor) - - 0.2 0.2 Phenolic antioxidant - 0.2 0.2 Bench IIID Oxidation Test
% Viscosity Increase (at 72 hrs) 349 42 0 17 L-3a Corr. Test, mg BWL 22.3 17.5 7.2 5.6
(1) The test oils (10W-30 grade) also contained 0.22% Ca from an overbased calcium sulfonate
+ 6.75% of a dispersant Vl improver + 0.05% of a pour point depressant in a solvent neutral
base oil.
Claims (21)
1. A composition of matter of the reaction product formed by reacting an alkenylsuccinimide (A) of the formula:
wherein R is an alkenyl radical having from 50 to 200 carbon atoms in the chain, and x is O to 10, with (B) an ammonium salt of a molybdenum thioacid or (C) a molybdenum oxyacid and hydrogen sulfide and removing any volatile by-products.
2. A composition as claimed in claim 1, wherein the ammonium salt of a molybdenum thioacid (B) is a preformed salt having 1 to 4 sulfur atoms per molybdenum atom, and the succinimide (A) is formed in situ.
3. A composition as claimed in claim 1, wherein the ammonium salt of a molybdenum thioacid is generated in situ by combining said succinimide with a molybdenum oxyacid followed by treatment with hydrogen sulfide, employing a mole ratio of H2S:Mo of at least 1:1.
4. A composition as claimed in claim 3, wherein the mole ratio H2S:Mo is 1:1 to 4:1.
5. A composition as claimed in claim 1 prepared by (1) reaction of an aqueous solution containing substantially equimolar amounts of ammonium tetrathiomolybdate with a solution of the alkenyl succinimide in a hydrocarbon solvent; (2) removal of water by azeotropic distillation, and (3) stripping off the organic solvent at reduced pressure.
6. A composition as claimed in claim 1, prepared by (1) reaction of an aqueous molybdic acid solution with substantially an equimolar amount of alkenylsuccinimide dissolved in a solvent mixture of a hydrocarbon and an ethylene glycol-based ether, (2) treatment of the resulting oxy-molybdenum derivative with 2 to 4 moles of hydrogen sulfide per mole of molybdenum, (3) removal of the water by azeotropic distillation, (4) filtering and, (5) stripping off any volatile solvents at reduced pressure.
7. A composition as claimed in claim 6, wherein the ethylene glycol-based ether is volatile.
8. A composition as claimed in claim 7, wherein the volatile ethylene glycol-based ether is diethylene-glycol dimethyl ether.
9. A composition as claimed in claim 6, wherein the ether is a non-volatile alkylphenyl ether of
ethyleneglycol or a polyethyleneglycol.
10. A composition as claimed in claim 9, wherein the non-volatile ether is a mono-nonylphenyl
ether of ethyleneglycol or of a polyglycol ether having 2 to 10 oxyethylene units.
11. A composition as claimed in claim 1, obtained by reacting substantially equimolar amounts of
(NH4)2MoS4 with an oil concentrate of the polybutenyl succinimide of triethylene-tetramine in an inert
solvent; boiling the resulting mixture to reflux, removing the water formed; filtering the water-free
reaction mixture and distilling off the solvent under reduced pressure.
12. A composition as claimed in claim 1, prepared by reacting an aqueous solution of Na2MoO4.2H20 and concentrated sulfuric acid to form molybdic acid; reacting the molybdic acid with
equimolar amounts of a polybutenylsuccinimide of triethylenetetramine in a solvent; bubbling H2S
therethrough; refluxing the resulting mixture; removing the water formed; removing any remaining
solids; and distilling off the solvent under reduced pressure.
13. A composition as claimed in claim 1 , wherein substantially equimolar amounts of an oil concentrate of a polybutenyl succinimide of triethylenetetramine and molybdic acid are reacted at less than 1 OOCC and atmospheric pressure then blown sequentially with H2S and then N2 while heating to a
temperature sufficient to remove water; heating at this temperature under reduced pressure and filtering to isolate the product.
14. A composition as claimed in claim 1, wherein the ammonium salt of a molybdenum thioacid
(B) is generated in situ by mixing said succinimide (A) with an aqueous solution of an ammonium salt of
an oxymolybdic acid followed by treatment with hydrogen sulfide employing a mole ratio of H2S:Mo of
1:1 to 4:1.
15. A composition as claimed in claim 14, wherein the aqueous solution of the ammonium salt of
the oxymolybdenum acid is generated by reaction of molybdenum trioxide with at least 1 mole of aqueous ammonium hydroxide.
16. A composition as claimed in claim 1, wherein the ammonium salt of a molybdenum thioacid
(B) is generated in situ by combining the succinimide with water, molybdenum trisxide, and from 0.1 to
0.5 mole of NH4OH per mole of molybdenum, followed by treatment with hydrogen sulfide employing a
mole ratio of H2S:Mo of 1:1 to 4:1.
17. A composition as claimed in claim 1, wherein the product has the formula:
wherein n= 1 to lO,x=Oto lO,y= 1 to4,z=3toOandm= 1 to lO,butnotgreaterthanx= 1;and
where I = 1 to 5, p = 0--2, and x, y, z and n have the preceding values.
18. A lubricant composition which comprises a mineral lubricating oil and from 0.01 to 55 weight percent of a composition as claimed in any of claims 1 to 17, said composition providing 0.01 to 5.0 percent weight of molybdenum.
19. A lubricant composition as claimed in claim 18, which comprises from 0.1 to 1 5.0 weight percent of the composition as claimed in any of claims 1 to 17.
20. A composition as claimed in claim 1 and substantially as hereinbefore described with reference to any of Examples 1 to 11.
21. A lubricant composition as claimed in claim 18 and substantially as hereinbefore described.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15904080A | 1980-06-13 | 1980-06-13 |
Publications (1)
Publication Number | Publication Date |
---|---|
GB2078230A true GB2078230A (en) | 1982-01-06 |
Family
ID=22570833
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB8115916A Withdrawn GB2078230A (en) | 1980-06-13 | 1981-05-22 | Thiomolybdenum derivatives of dispersant alkenylsuccinimides and lubricants containing same |
Country Status (6)
Country | Link |
---|---|
JP (1) | JPS5716095A (en) |
BE (1) | BE889177A (en) |
DE (1) | DE3122918A1 (en) |
FR (1) | FR2484441A1 (en) |
GB (1) | GB2078230A (en) |
IT (1) | IT1137088B (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2460323A1 (en) * | 1979-06-28 | 1981-01-23 | Chevron Res | PROCESS FOR PRODUCING A SULFIDE COMPOUND CONTAINING MOLYBDENE, COMPOUND OBTAINED AND LUBRICATING OIL CONTAINING THE SAME |
FR2460324A1 (en) * | 1979-06-28 | 1981-01-23 | Chevron Res | PROCESS FOR PRODUCING A MOLYBDEN-CONTAINING COMPOUND, PRODUCT OBTAINED, AND LUBRICATING OIL COMPOSITION CONTAINING THE SAME |
WO2002042397A1 (en) * | 2000-11-22 | 2002-05-30 | Idemitsu Kosan Co., Ltd. | Metal working fluid composition |
EP2297284A2 (en) * | 2008-06-30 | 2011-03-23 | Chevron Oronite Company LLC | Lubricating oil additive and lubricating oil composition containing same |
EP2300579A2 (en) * | 2008-06-30 | 2011-03-30 | Chevron Oronite Company LLC | Lubricating oil additive and lubricating oil composition containing same |
US8592355B2 (en) | 2005-06-17 | 2013-11-26 | Idemitsu Kosan Co., Ltd. | Engine oil composition |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4369119A (en) * | 1981-04-03 | 1983-01-18 | Chevron Research Company | Antioxidant combinations of molybdenum complexes and organic sulfur compounds for lubricating oils |
US4370246A (en) * | 1981-04-27 | 1983-01-25 | Chevron Research Company | Antioxidant combinations of molybdenum complexes and aromatic amine compounds |
RU2287556C2 (en) * | 2000-06-02 | 2006-11-20 | Кромптон Корпорейшн | Molybdenum sulfide and its derivatives nanosize particles and their using |
US6962896B2 (en) * | 2002-05-31 | 2005-11-08 | Chevron Oronite Company Llc | Reduced color molybdenum-containing composition and a method of making same |
JP4991133B2 (en) * | 2005-09-14 | 2012-08-01 | 三洋化成工業株式会社 | Antioxidant improver for lubricant and lubricant composition |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3223625A (en) * | 1963-11-12 | 1965-12-14 | Exxon Research Engineering Co | Colloidal molybdenum complexes and their preparation |
CA1125735A (en) * | 1978-09-18 | 1982-06-15 | Esther D. Winans | Molybdenum complexes of ashless nitrogen dispersants as friction reducing antiwear additives for lubricating oils |
CA1174032A (en) * | 1979-06-28 | 1984-09-11 | John M. King | Process of preparing molybdenum complexes, the complexes so produced and lubricants containing same |
CA1152315A (en) * | 1979-06-28 | 1983-08-23 | Louis Devries | Molybdenum compounds (vll) |
-
1981
- 1981-05-20 JP JP7508281A patent/JPS5716095A/en active Pending
- 1981-05-22 GB GB8115916A patent/GB2078230A/en not_active Withdrawn
- 1981-06-05 FR FR8111144A patent/FR2484441A1/en active Pending
- 1981-06-10 DE DE19813122918 patent/DE3122918A1/en not_active Withdrawn
- 1981-06-11 BE BE0/205064A patent/BE889177A/en not_active IP Right Cessation
- 1981-06-12 IT IT22297/81A patent/IT1137088B/en active
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2460323A1 (en) * | 1979-06-28 | 1981-01-23 | Chevron Res | PROCESS FOR PRODUCING A SULFIDE COMPOUND CONTAINING MOLYBDENE, COMPOUND OBTAINED AND LUBRICATING OIL CONTAINING THE SAME |
FR2460324A1 (en) * | 1979-06-28 | 1981-01-23 | Chevron Res | PROCESS FOR PRODUCING A MOLYBDEN-CONTAINING COMPOUND, PRODUCT OBTAINED, AND LUBRICATING OIL COMPOSITION CONTAINING THE SAME |
WO2002042397A1 (en) * | 2000-11-22 | 2002-05-30 | Idemitsu Kosan Co., Ltd. | Metal working fluid composition |
US8592355B2 (en) | 2005-06-17 | 2013-11-26 | Idemitsu Kosan Co., Ltd. | Engine oil composition |
EP2297284A2 (en) * | 2008-06-30 | 2011-03-23 | Chevron Oronite Company LLC | Lubricating oil additive and lubricating oil composition containing same |
EP2300579A2 (en) * | 2008-06-30 | 2011-03-30 | Chevron Oronite Company LLC | Lubricating oil additive and lubricating oil composition containing same |
EP2300579A4 (en) * | 2008-06-30 | 2012-05-23 | Chevron Oronite Co | Lubricating oil additive and lubricating oil composition containing same |
EP2297284A4 (en) * | 2008-06-30 | 2012-05-23 | Chevron Oronite Co | Lubricating oil additive and lubricating oil composition containing same |
Also Published As
Publication number | Publication date |
---|---|
FR2484441A1 (en) | 1981-12-18 |
DE3122918A1 (en) | 1982-04-29 |
BE889177A (en) | 1981-12-11 |
JPS5716095A (en) | 1982-01-27 |
IT1137088B (en) | 1986-09-03 |
IT8122297A0 (en) | 1981-06-12 |
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